Cosmetic composition for treating hair

ABSTRACT

A cosmetic composition for treating hair comprising an electrophile methylol amine and a urein compound, one or both of which contain a chemical group which has cosmetic properties; and a method of treating hair with this composition. The compounds having the formula IN WHICH N 1 OR 2, X is O, S or NH and Y is a disulfide, carboxylic acid, tertiary or quaternary amine or -SH group which has cosmetic properties.

United States Patent Kalopissis et al.

[ Feb. 15, 1972 [54] COSMETIC COMPOSITION FOR TREATING HAIR [72] Inventors: Gregoire Kalopissis, Paris; Jean-Louis Abegg, Ie Perreaux; Guiliana Ghilardi; Henri Philippe de Beaulieu, both of Paris, all of France [52] US. Cl ..8/127.5l, 8/127.5, 8/127.6, 424/71, 424/72 [51] Int. Cl ..A6lk 7/08, A61k 7/10 [58] Field ofSearch .8/127.51, 127.6, 127.5; 424/71, 72

[56] References Cited UNITED STATES PATENTS 3,534,135 10/1970 Wajaroff ..424/71 3,349,000 10/1967 Joos ..424/7l 3,232,933 2/1966 Giindel ..260/247.1

Primary Examiner-George F. Lesmes Assistant Examiner-B. Bettis Attorney-Holcombe, Wetherill and Brisebois ABSTRACT A cosmetic composition for treating hair comprising an electrophile methylol amine and a urein compound, one or both of which contain a chemical group-which has cosmetic properties; and a method of treating hair with this composition.

The compounds having the formula:

Y(NH(l'TNHz)n .s .a.A Y-. X in which n=1 or 2, X is O, S or NH and Y is a disulfide, carboxylic acid, tertiary or quaternary amine or SH group which has cosmetic properties.

6 Claims, No Drawings This invention relates to a cosmetic composition which ,makes it possible to improve the condition of human hairand to impart thereto certain properties which are useful when it is to be subjected to a subsequent cosmetic treatment.

It is known that hair is more or less degraded by atmospheric agents such as sea water, or'the sun, or as a consequence of chemical treatments such as permanent waves-and bleachings.

The effects of such degradations may be to a large extent eliminated by using the compositions according to the invention.

It has already been suggested, in order to improve the strength and elasticity of the hair, that it be treated with compositions containing dimethylolurea or dimethylolthiourea so as to obtain the desired result by polymerization and condensation of these active compounds on the keratin in the presence of an acid catalyst, under the influence of heat.

It has likewise been suggested that compositions comprising methylol products which are more stable than dimethylolurea and dimethylolthiourea be used, which products yield excellent results due to polymerization in'the keratin chain and condensation of these compounds on the reactive groups of the keratin, thereby in practice imparting to the treated hair greater strength, an improved appearance and, in general, attractive cosmetic properties. 7

It is also known that it is desirable, to not only strengthen the keratinic fiber by means of the above process, but also to impart thereto a greater capacity to react with various products used in the cosmetic treatment of hair.

in articular, it has been found desirable to attach inside the hair compounds having disulfide bonds. These additional -8 bonds result in a new and valuable behavior of the fiber with respect to chemicals conventionally used in the treatment thereof, such as reducing solutions containing mercaptans or sulfites, and oxidizing agents containing hydrogen peroxide, for example.

In like manner, attempts have been made to attach carboxylic groups inside the hair. This addition of acid groups increases the affinity of the fiber for basic dyes.

On the other hand, basicgroups, or even fatty chains, have been introduced into the hair in order to increase the affinity of the hair for acid dyes, or durably improve the sheen and feel of the hair.

This list is by no means exhaustive and the number of cosmetic substituents or additives which it may be desirable to attach to the keratin of the hair is quite long.

Applicants have found that, in a surprising manner, the polycondensation of methylol compounds in the presence of compounds of the urein type leads to a compound or mixture of compounds having a rather high molecular weight containing the skeletons of both the methylol and urein compounds.

This phenomenon is particularly valuable when the compound of the urein type contains a cosmetic component attached to the nitrogen which is finally embedded inside the hair when the methylol compounds are polymerized in the keratin in the presence of these particular urein compounds.

This makes it possible to introduce into the hair reactive groups which are cosmetically valuable in that they strengthen the hair and particularly improve its mechanochemical properties after the polycondensation.

It is the object of the present invention to provide a composition for treating or modifying keratinic fibers essentially characterized by the fact that it comprises in combination at least one methylol compound comprising at least one group responding to the formula:

h ydroxymethyl radical, or an alkoxymethyl radical, R represents either hydrogen, or a lower alkyl radical,

E represents a radical which is sufficiently electrophile to assure that the entire g'rou molecule,

5 and at least-one urein compound responding to the followin which:

n=1 or 2 X represents oxygen, sulfur, 'or an N H radical,

Y represents hydrogemor a monovalent or divalent organic radical depending on whether n=l or 2.

ing of a disulfide function,

SH function.

In a preferred "embodiment of the invention, E is selected from among the following groups:

ILIH ll- Among the methylol groups which may be used in the composition according to the invention are:

monomethylolurea, responding to the formula:

dimethylolurea, responding to the formula:

H0 OH NH-fi-NIFCHZO H monomethylolthiourea, responding to the formula:

1-10 CI-Iz-NI-Ffi-NH;

'drmethylolthrourea, responding tothe formula:

H0 CH2NH%|7NHCH2OH monomethyloldicyandiamide, responding to the formula:

NECNHfiJ-NHCH:OH NH trimethylol melamine, responding to the formula:

(IJHzOH IIVH if i HOHzC-NH-C CNH-CH2OH '5 l l N-,N-methyl, methylolurea, responding to the formula:

H0 CIl:NCIl=--(|!-NH2 N,N-dimethylolurea, responding to the formula:

p is sufli'ciently chemically stable 'to prevent the immediate release of a formol CHgOH CHzOH dimethylolethylene thiourea, responding to the formula:

CHzOH onion methoxymethyl dicyandiamide, responding to the formula:

NEONH-CNHCHzO CHa H dimethylol dihydroxy ethylene-urea N,N'-(dimethylol dicarbamyl) cystamine, responding to the formula:

(diethyl, monomethylolethylurea )-ammonium iodide:

methyl,

Et Me Among the urein-type compounds which may be used in the cosmetic compositions according to the invention are:

hydantoic acid, responding to the formula:

thiourea, respondingto the formula:

N-methyl-dipropylurea. responding to the formula:

(dimethyl-copra-ethylurea)-ammonium chloride responding to the formula:

N,N-carbamyl cystamine, responding to the formula:

compound responding to the formula:

HO O C CHzNH|Cl-NHz compound responding to the formula:

N-carbamyl cysteamine, responding to the formula: 1

' HSCH -CH --NHCO-NH N-carbamyl cystamine hydrochloride responding to the formula:

N,N'-(dimethyl-ethylurea) cystamine dichloride:

(diethyl-methyl-ethylurea )-ammonium iodide responding to the formula:

diethylamino ethylurea, responding to the formula:

The composition according to the invention may advantageously contain from= 0.5 to l2 percent and preferably 2 from l to 4 percent by weight of methylol compounds.

In a preferred embodiment of the invention the number of urea groups carried by the urein-type compound lies between 0.2 and 3 times and preferably from 0.5 to 1.0 times the number of hydroxyrnethyl or alkoxy methyl groups carried by the methylol compound.

I In one specific embodiment of the inyention, the composition also contains an acid catalyst, which may bea rnineralor organic acid used inthe cosmetic fieldor a salthaving anacid reaction.

The composition according to the invention may take the form of an aqueous or hydroalcoholic solution and serve as a setting lotion which may comprise any additives conventionallyincluded in such lotions The composition according to the'invention may also .take the form of a gel or cream, or be packaged in aerosolf'orm.

The composition according to the inventionmay also contain any ingredients conventionally used incosmetics, such as dyes, perfumes, surface-active agents, swelling agents, resins, etc.

In one specific embodiment of the invention, the composition may be packaged in two phases, a solid phase containing the methylol compounds, and the urein-type compounds, and a liquid phase which is an aqueous or hydroalcoholic solution, which may contain conventional cosmetic additives and/or an acid catalyst.

In another version of this method of packaging this product, the solid phase contains only the methylol compounds, and the urein-type compounds are in aqueous or hydroalcoholic solution.

In this embodiment, the cosmetic composition according to the invention is prepared at the moment of use by dissolving the solid phase in the liquid phase. This rnethod of packaging makes it possible to avoid the premature polycondensations which may take place during prolonged storage of the composition. i

In particular, the solid phase or the aqueous phase of the cosmetic composition packaged in this manner may also contain a salt of sulfurous acid, such as sodium metabisultite.

A further object of the present invention is to provide a method of treating hair characterized by the fact that the hair is impregnated with the above-described composition, and then dried by heating, after having first been rinsed.

In a first method of carrying out this process, the cosmetic composition does not itself contain the acid catalyst necessary to bring about polycondensation of the methylol compounds and the urein-type compounds in the keratinic fiber, and this acid catalyst is instead applied to the hair either before or after the composition according to the invention.

In another method of carrying out this process a cosmetic composition which already contains the acid polymerization catalyst is directly applied to the hair, which is then dried as has already been described.

I The treatment of the hair with the composition according to the invention leads to two results. On the one hand, it

strengthens=the keratinic fiber by I forming a polymer inside that fiberv and, on the other hand, pennits the introduction and attachment of reactive groups inside the keratinic fiber. These reactivegroups advantageously modify the reactivity of the keratin with respect to other cosmetic reagents.

lt isa further object of the present invention to provide the new article of manufacture .which consists of a compound responding to the following formula:

in which:

X represents hydrogen, sulfur, or an NH radical,

Y is a. radical comprising a chemical-functionwhich enables it to serve a cosmeticrpurpose such, for example, as a disulfide function, a carboxylic acid function, a tertiaryor .quatemary amine function, a .fatty chain, or an SH function.

The present invention has ,as its particular object the production of a new-article of manufactureconsisting of a compound selected from thegroup consisting of:

N-methyl-dipropylurea, (dimethyl-copra-ethylurea)-ammonium-chloride, N,N-carbamyl cystamine, N-carbamyl-cystamine hydrochloride, N,N'-(dimethyl-ethylurea)- cystamine dichloride, (diethyl-methyl-ethylurea)-ammonium iodide, diethylamino ethylurea (dimethyl, .dipropylurea) ammonium methosulfate,and N-carbamyl cysteamine.

A further object of the present invention is to provide a new method of preparing urein-type compounds as described above, characterizedby the fact that a cyanate or an alkaline thiocyanate .is reacted with amine compounds having a Y- grouprepresenting the cosmetic additive in question attached to the nitrogen.

in a particular method of carrying out the invention, the amine which carries the cosmetic additive attached to its nitrogen atom is reacted .with urea, to produce the corresponding urein by elimination of ammonia.

In another method of carrying out the invention, a tertiary amine having a cosmetic additive attached to its nitrogen atom is reactedwith a halogenoalkylurea.

In order that the invention may be better understood, several examples of the use of compositions according to the invention will now be described, purely by way of illustration.

EXAMPLE 1 An aqueous solution of the following composition is applied to natural hair which has first been washed and dried:

monomethylolurea 3.6 g. hydantoic acid l.l8 g. water, q.s.p. cc.

The hair is then set in aconventional manner by winding it up on rollers and drying it under a hood at a temperature of 45 -50 C. This attaches to the keratin of the hair an acid compound having the following statistical formula:

dyes than natural, or untreated hair. It is also strengthened and the set holds well and is springy.

EXAMPLE 2 A solution of the following composition is applied to hair which has been bleached:

wound up on rollers for 30 minutes at 45 and 50 C.

This operation permits the attachment to the keratin of a compound of the disulfide typewhich is soluble in reducing media and has substantially the following composition:

In this formula:

n lies between 0.5 and l inclusive.

The hair is strengthened and the set holds well and is sprin- 8% Moreover, the presence of artificial disulfide bonds in the kcrutinic libcr makes it possible to subsequently permanently wave or bleach the hair under improved conditions.

EXAMPLE 3 Natural hair which has first been washed and dried is treated with a solution having the following composition:

monomethylolurea 3.6 g. N-methyl-dipropylurea 2.3 g. hydrochloric acid, q.s.p. pH 2.5

I cc.

water, q.s.p.

The hair is then set in a conventional manner, keeping it for about 30 minutes at a temperature between 45 and 50 C.

This procedure leads to the attachment of a cationic condensate to the keratinic fiber which has the advantage that it may thereafter be very easily removed by simple shampooing.

On the other hand, the hair has been strengthened and the set" is of excellent quality.

EXAMPLE 4 In the case of hair which has previously been bleached, and which is now to be permanently waved, the hair is first impregnated with the following composition:

monomethylolurea 8 g. (dimethyl-copra-ethylurea)-ammonium chloride 2 g. acetic acid q.s.p. pH 3 water q.s.p. I00 cc.

EXAMPLE 5 Preparation of (dimethyl-dipropylurea)-amrnonium methosulfate The first step is to prepare N-methyl-dipropylurea by reacting potassium cyanate with N-methyl-dipropylamine dihydrochloride in stoichiometric proportions. The reaction is carried out in aqueous solution at a temperature of 90 C. for 2 hours.

The product is dried by evaporation and then extracted with hot absolute ethanol. The result is a white powder titrating 95 a temperature between percent of the theoretical amount of total ry amines.

One mol of N-methyl-dipropylurea is suspended in l liter of absolute ethanol. A stoichiometric quantity, or a slight excess, of methyl sulfate is added slowly, while stirring. The resulting quaternary compound separates from the alcoholic layer, in the form of a thick oil which is vacuum dried and may be purified by washing with ether. The yield is practically quantitative'.

amines and of tertia- EXAMPLE 6 Preparation of N,N-(dimethyl-ethylurea)-cystamine dichloride 7 One mol of chloroethylurea is prepared in a conventional manner by reacting potassium cyanate with chloroethylamine hydrochloride, and then dissolving the product in ethanol at 70 C. 0.5 mol of tetramethyl cystamine, prepared by alkaline hydrolysis of the reaction product of sodium thiosulfate and bromo-diethylamino ethane hydrobromide is then added. The mixture is heated for 3 hours and 30 minutes, at C., and the solvent then evacuated under vacuum. The product is dried on phosphoric anhydride'. The resulting paste is washed with 450 cc. of chloroform, and again dried on phosphoric anhydride. The final result is a 98 percent yield of a solid white product titrating about percent of the theoretical value of disulfide and ionized chloride.

What is claimed is:

l. A process for treating human hair which comprises applying to said hair a composition containing in a solvent selected from the group consisting of water and'hydroalcoholic solution:

I. at least one compound selected from the group consisting of monomethylolurea, dimethylolurea, monomethylol 'thiourea, dimethylol thiourea, monomethylol dicyandiamide, trimethylol melamine, bismethoxymethyl urea, dimethylol ethylene urea, dimethylol ethylene thiourea, methoxymethyl dicyandiamide, dimethylol dihydroxy ethylene urea, N,N'-(dimethylol dicarbamyl) cystamine. (diethylmethylmonomethylol. ethylurea)-ammonium iodide, N,N-methylolurea and N,N-dimethylolurea, and

2. at least a urein compound corresponding to the formula:

in which:

X is selected from the group consisting of O, S and NH, n is l or 2 and when n is 1, Y is selected from the group conand when n is 2, Y is selected from the group consisting of *(CH2)al T( 2)a-, 2)2 H2)Z CH CH said composition containing said compound (I) in a concentration ranging from 0.5 to 12 percent by weight, polycondensing said compound and said urein compound on said hair in the presence of an acid catalyst in amounts sufficient to polycondense said compound and said urein compound, rinsing the hair and then drying the same.

2. The process of claim 1 wherein said acid catalyst is selected from the group consisting of acetic acid, phosphoric acid and hydrochloric acid.

3. The process of claim 1 wherein said acid catalyst is applied to the hair prior to the application of said composition to the hair.

4. The process of claim 1 wherein said acid catalyst is applied to the hair subsequent to the application of said composition to the hair but before rinsing said hair.

5. The process of claim 1 wherein said acid catalyst is applied to the hair concurrently with the application of said composition to the hair.

6. The process of claim 1 wherein said urein compound is r a compound having the formula N-carbamyl N-carbamyl cysteamine, cystamine hydrochloride, N,N dimethyl-ethylurea )cystamine dichloride, (diethyl-methyl-ethylurea )-ammonium iodide, diethylamino ethylurea and (dimethyl-dipropylurea)-ammonium methosulfate. 

2. at least a urein compound corresponding to the formula: in which: X is selected from the group consisting of O, S and NH, n is 1 or 2 and when n is 1, Y is selected from the group consisting of hydrogen,
 2. The process of claim 1 wherein said acid catalyst is selected from the group consisting of acetic acid, phosphoric acid and hydrochloric acid.
 3. The process of claim 1 wherein said acid catalyst is applied to the hair prior to the application of said composition to the hair.
 4. The process of claim 1 wherein said acid catalyst is applied to the hair subsequent to the application of said composition to the hair but before rinsing said hair.
 5. The process of claim 1 wherein said acid catalyst is applied to the hair concurrently with the application of said composition to the hair.
 6. The process of claim 1 wherein said urein compound is selected from the group consisting of hydantoic acid, thiourea, N-methyl-dipropyl urea, (dimethyl-copra-ethylurea)-ammonium chloride, N,N''-carbamyl cystamine, a compound having the formula a compound having the formula N-carbamyl cysteamine, N-carbamyl cystamine hydrochloride, N,N''-(dimethyl-ethylurea)cystamine dichloride, (diethyl-methyl-ethylurea)-ammonium iodide, diethylamino ethylurea and (dimethyl-dipropylurea)-ammonium methosulfate. 